EP0160616B1 - Use of a steel in atmospheres containing hydrogen sulfide - Google Patents

Use of a steel in atmospheres containing hydrogen sulfide Download PDF

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Publication number
EP0160616B1
EP0160616B1 EP85730016A EP85730016A EP0160616B1 EP 0160616 B1 EP0160616 B1 EP 0160616B1 EP 85730016 A EP85730016 A EP 85730016A EP 85730016 A EP85730016 A EP 85730016A EP 0160616 B1 EP0160616 B1 EP 0160616B1
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Prior art keywords
cooled
steel
pipes
temperature
air
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Expired
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EP85730016A
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German (de)
French (fr)
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EP0160616A2 (en
EP0160616A3 (en
Inventor
Ingo Dr.-Ing. Von Hagen
Hans-Georg Dr.-Ing. Hillenbrand
Rolf Konrad Dr.-Ing. Pöpperling
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Vodafone GmbH
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Mannesmann AG
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Priority to AT85730016T priority Critical patent/ATE38059T1/en
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/10—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of tubular bodies

Definitions

  • a steel is known with alloy areas of the elements C, Mn, Si, Cr, V, N, of which the current one is a selection (DE-OS 31 27 373). From such steels it is known that the finished product has a yield strength between 480 and 650 N / mm2 with a special deformation and temperature control.
  • the special feature is that during tube production the hollow body is cooled to a temperature between Ac1 and plus 500 ° C before the final longitudinal rolling and then heated to a temperature above Ar3 as the last rolling section to reduce the stretch.
  • quality level N 80 is neither required nor guaranteed that the product, when used in media containing hydrogen sulfide, generally has sufficiently reliable resistance to stress corrosion cracking.
  • quality level L 80 is prescribed for use under sour gas conditions according to API, which has limited technological properties compared to quality level N 80 and a limitation of hardness to a maximum of HRC 22 and a remuneration structure.
  • the tempering consists of quench hardening and subsequent tempering. The high expenditure of energy and time for the treatment and reworking of the product is perceived as a disadvantage.
  • the invention is based on the above steel alloy and the production of pipes therefrom. It has set itself the task of selecting alloy ranges and of carrying out the heat treatment in such a way that a fine-grained ferritic pearlitic structure is produced which has comparable stress corrosion cracking resistance as a tempered structure with comparable yield strengths.
  • ferritic-pearlitic steels Due to a higher ratio of yield strength to tensile strength of tempered compared to ferritic-pearlitic steels, ferritic-pearlitic steels have a higher tensile strength and thus hardness with the same yield strength.
  • the structures of the steels mentioned in claim 1 have a maximum hardness of HRC 26. At the same time, these steels have comparable resistance to stress corrosion cracking to tempered steels with HRC 22. However, this condition has not been practiced with the previously usual materials, which also achieve the required mechanical strength, and has also not become known in the literature.
  • the current proposal avoids the subsequent tempering and specifies an alloy selection for a steel that cools in air from the hot forming heat and, if necessary, undergoes normalization treatment during the hot rolling process and fulfills requirements for a narrow yield strength range as well as for high resistance to hydrogen-induced stress corrosion cracking. This results in a simplified production of a product for use in an atmosphere containing hydrogen sulfide.
  • the hardness was HRC 23 and the average grain size was ASTM 10.

Abstract

A ferritic perlite steel is used for pipes and tubing to be highly resistant against stress corrosion cracking when exposed to H2S, and having following alloying range, all percentages by weight: from 0.3 to 0.45 C, from 1.4 to 1.8 Mn, from 0.2 to 0.5 Si, from 0.2 to 0.5 Cr, from 0.04 to 0.1 V, up to 0.06 Nb, </=0.003 S, the remainder being iron whereby the combined Niobium and Vandium content must obey the rule that the sum of the V content plus twice the Nb content must not be not less than 0.1%; tubing is made by hot working followed by cooling in air from the final temperature attained during hot working, so that a texture and grain size in accordance with ASTM finer than 8 obtains; the tubing has strength value of 552 N/mm2</=0.2% of rupture elongation limit </=655 N/mm2 and a tensile strength exceeding 655 N/mm2.

Description

Bekannt ist ein Stahl mit Legierungsbereichen der Elemente C, Mn, Si, Cr, V, N, von denen der gegenwärtige eine Auswahl ist (DE-OS 31 27 373). Von derartigen Stählen ist es bekannt, daß bei einer besonderen Verformungs- und Temperaturführung das fertige Produkt eine Streckgrenze zwischen 480 und 650 N/qmm besitzt. Die Besonderheit besteht darin, daß bei der Rohrherstellung der Hohlkörper vor dem abschließenden Längswalzen auf eine Temperatur zwischen Ac1 und plus 500 °C abgekühlt und danach zum Streckreduzieren als letzten Walzabschnitt auf eine Temperatur über Ar3 erwärmt wird. Dieses Produkt entspricht den Qualitätsbedingungen der API-Spezifikation N .80. (APJ = American Petroleum Institute)A steel is known with alloy areas of the elements C, Mn, Si, Cr, V, N, of which the current one is a selection (DE-OS 31 27 373). From such steels it is known that the finished product has a yield strength between 480 and 650 N / mm² with a special deformation and temperature control. The special feature is that during tube production the hollow body is cooled to a temperature between Ac1 and plus 500 ° C before the final longitudinal rolling and then heated to a temperature above Ar3 as the last rolling section to reduce the stretch. This product meets the quality requirements of API specification N .80. (APJ = American Petroleum Institute)

Von der Gütestufe N 80 wird aber weder verlangt noch gewährleistet, daß das Produkt in schwefelwasserstoffhaltigen Medien eingesetzt generell hinreichend zuverlässige Beständigkeit gegen Spannungsrißkorrosion besitzt. Deswegen ist für den Einsatz unter Sauergasbedingungen nach API die Gütestufe L 80 vorgeschrieben, die gegenüber der Gütestufe N 80 eingeschränkte technologische Eigenschaften und eine Begrenzung der Härte auf maximal HRC 22 und ein Vergütungsgefüge aufweist. Das Vergüten besteht aus einem Abschreckhärten und nachfolgendem Anlassen. Der hohe Energie- und Zeitaufwand für die Behandlung und die Nacharbeit des Produktes wird als Nachteil empfunden.However, quality level N 80 is neither required nor guaranteed that the product, when used in media containing hydrogen sulfide, generally has sufficiently reliable resistance to stress corrosion cracking. For this reason, quality level L 80 is prescribed for use under sour gas conditions according to API, which has limited technological properties compared to quality level N 80 and a limitation of hardness to a maximum of HRC 22 and a remuneration structure. The tempering consists of quench hardening and subsequent tempering. The high expenditure of energy and time for the treatment and reworking of the product is perceived as a disadvantage.

Die Erfindung geht aus von der vorstehenden Stahllegierung und der Herstellung von Rohren daraus. Sie hat sich die Aufgabe gestellt, Legierungsbereiche auszuwählen und die Wärmebehandlung so zu führen, daß ein feinkörniges ferritisches perlitisches Gefüge erzeugt wird, das vergleichbare Spannungsrißkorrosionsbeständigkeit wie vergütetes Gefüge mit vergleichbarer Streckgrenzen aufweist.The invention is based on the above steel alloy and the production of pipes therefrom. It has set itself the task of selecting alloy ranges and of carrying out the heat treatment in such a way that a fine-grained ferritic pearlitic structure is produced which has comparable stress corrosion cracking resistance as a tempered structure with comparable yield strengths.

Aufgrund eines höheren Verhältnisses von Streckgrenze zu Zugfestigkeit von vergüteten im Vergleich zu ferritisch-perlitischen Stählen weisen ferritisch-perlitische Stähle bei gleicher Streckgrenze eine höhere Zugfestigkeit und damit Härte auf. Die Gefüge der im Anspruch 1 genannten Stähle weisen maximal Härten von HRC 26 auf. Gleichzeitig besitzen diese Stähle vergleichbare Spannungsrißkorrosionsbeständigkeit wie Vergütungsstähle mit HRC 22. Diese Bedingung ist aber mit den bislang üblichen Werkstoffen, die die außerdem geforderte mechanische Festigkeit erreichen, nicht praktiziert und auch nicht in der Literatur bekanntgeworden.Due to a higher ratio of yield strength to tensile strength of tempered compared to ferritic-pearlitic steels, ferritic-pearlitic steels have a higher tensile strength and thus hardness with the same yield strength. The structures of the steels mentioned in claim 1 have a maximum hardness of HRC 26. At the same time, these steels have comparable resistance to stress corrosion cracking to tempered steels with HRC 22. However, this condition has not been practiced with the previously usual materials, which also achieve the required mechanical strength, and has also not become known in the literature.

Der gegenwärtige Vorschlag vermeidet das nachträgliche Vergüten und benennt eine Legierungsauswahl für einen Stahl, der aus der Warmformgebungshitze an Luft abgekühlt und ggf. während der nach dem Warmwalzvorgang eine Normalisierungsbehandlung erfährt und sowohl Forderungen nach einem engen Streckgrenzenbereich als auch nach hoher Beständigkeit gegen wasserstoffinduzierte Spannungsrißkorrosion erfüllt. Es ergibt sich somit eine vereinfachte Herstellung eines Produktes für die Verwendung in schwefelwasserstoffhaltiger Atmosphäre.The current proposal avoids the subsequent tempering and specifies an alloy selection for a steel that cools in air from the hot forming heat and, if necessary, undergoes normalization treatment during the hot rolling process and fulfills requirements for a narrow yield strength range as well as for high resistance to hydrogen-induced stress corrosion cracking. This results in a simplified production of a product for use in an atmosphere containing hydrogen sulfide.

Nachfolgend wird ein Ausführungsbeispiel näher erläutert.

Figure imgb0001
der somit unter die in Anspruch 1 genannte Zusammensetzung fällt, ist auf die Walztemperatur 1 250 °C aufgeheizt und anschließend auf die Rohrabmessung 139,7 x 7,7 mm gewalzt worden. Vor dem letzten Walzabschnitt ist auf eine Temperatur von unter 550 °C bis zur völligen Umkörnung abgekühlt und anschließend wieder auf eine Walztemperatur von 920 °C aufgeheizt worden. Nach dem Fertigwalzen ist aus der Walzhitze an Luft abgekühlt worden.An exemplary embodiment is explained in more detail below.
Figure imgb0001
 which thus falls under the composition mentioned in claim 1, has been heated to the rolling temperature 1 250 ° C and then rolled to the tube dimensions 139.7 x 7.7 mm. Before the last rolling section, the temperature was reduced to below 550 ° C. until the grain was completely grained and then heated again to a rolling temperature of 920 ° C. After the finish rolling, air was cooled from the rolling heat.

Die Festigkeitskennwerte stellen. sich wie folgt dar:

Figure imgb0002
Set the strength values. are as follows:
Figure imgb0002

Die Härte lag bei HRC 23 und die Korngröße betrug im Mittel ASTM 10.The hardness was HRC 23 and the average grain size was ASTM 10.

Die anschließend durchgeführte Prüfung auf Beständigkeit gegen wasserstoffinduzierte Spannungsrißkorrosion in einer schwefelwasserstoffhaltigen Lösung mit pH = 3 ergab nach 1 OOOstündiger Versuchsdauer eine kritische Grenzspannung für Spannungsrißkorrosion von 40% der Streckgrenze. Diese Grenzspannung liegt somit, wie aus der beigefügten Figur zu entnehmen ist, im Streuband für vergütete Kohlenstoff-Mangan-Stähle gleicher Festigkeitsstufe mit HRC s= 22.The subsequent test for resistance to hydrogen-induced stress corrosion cracking in a hydrogen sulfide-containing solution with pH = 3 resulted in a critical limit stress for stress corrosion cracking of 40% of the yield stress after a test period of 1 hour. This limit stress is, as can be seen from the attached figure, in the scatter band for tempered carbon-manganese steels of the same strength level with HRC s = 22.

Claims (3)

1. Use of a ferritic-pearlitic steel with the composition in percentage mass
Figure imgb0006
remainder Fe; the dependence for the niobium and vanadium contents being % V + 2 x % Nb
Figure imgb0007
0.1, from which pipes are produced by hot shaping, which are cooled from the hot shaping heat in air, so that the structure has an ASTM grain size finer than 8 and the product has the following strength values :
Figure imgb0008
Figure imgb0009
for pipes are required to have high resistance to stress corrosion cracking in media containing hydrogen sulphide.
2. Use of a steel for the purpose according to Claim 1, in which the pipes from the hot shaping heat undergo a normalisation treatment, being cooled to a temperature of less than 600 °C to room temperature, subsequently re-heated to over 850 °C and then cooled in air.
3. Use of a steel for the purpose according to Claim 1, in which the pipes are cooled to a temperature of less than 600 °C to 400 °C during the rolling process before the last rolling section, are heated from this temperature to over 850 °C, finished-rolled and cooled in air.
EP85730016A 1984-04-24 1985-02-01 Use of a steel in atmospheres containing hydrogen sulfide Expired EP0160616B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT85730016T ATE38059T1 (en) 1984-04-24 1985-02-01 USE OF A STEEL IN HYDROGEN SULFIDE ATMOSPHERE.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19843415590 DE3415590A1 (en) 1984-04-24 1984-04-24 USE OF A STEEL IN HYDROGEN-LIQUID
DE3415590 1984-04-24

Publications (3)

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EP0160616A2 EP0160616A2 (en) 1985-11-06
EP0160616A3 EP0160616A3 (en) 1986-12-30
EP0160616B1 true EP0160616B1 (en) 1988-10-19

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EP85730016A Expired EP0160616B1 (en) 1984-04-24 1985-02-01 Use of a steel in atmospheres containing hydrogen sulfide

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US (1) US4631095A (en)
EP (1) EP0160616B1 (en)
JP (1) JPS60234952A (en)
AT (1) ATE38059T1 (en)
BR (1) BR8501925A (en)
CA (1) CA1239332A (en)
DE (1) DE3415590A1 (en)

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DE3909675A1 (en) * 1989-03-23 1990-09-27 Siemens Ag Barring of DTMF subscriber numbers
DE4019118C1 (en) * 1990-06-12 1991-04-18 Mannesmann Ag, 4000 Duesseldorf, De
DE4439059A1 (en) * 1994-11-02 1996-05-09 Teves Gmbh Alfred Closing device for closing pressure-carrying channels in a housing
BR9804879A (en) * 1997-04-30 1999-08-24 Kawasaki Steel Co High ductility steel product, high strength and process for its production
US5993570A (en) * 1997-06-20 1999-11-30 American Cast Iron Pipe Company Linepipe and structural steel produced by high speed continuous casting
WO1999000525A1 (en) * 1997-06-26 1999-01-07 Kawasaki Steel Corporation Ultrafine-grain steel pipe and process for manufacturing the same
ATE312208T1 (en) * 1997-06-26 2005-12-15 Jfe Steel Corp METHOD FOR PRODUCING STEEL PIPE WITH ULTRA FINE STRUCTURE
US6149862A (en) * 1999-05-18 2000-11-21 The Atri Group Ltd. Iron-silicon alloy and alloy product, exhibiting improved resistance to hydrogen embrittlement and method of making the same
JP2006083963A (en) * 2004-09-16 2006-03-30 Ntn Corp Hollow power transmission shaft
CN102400057B (en) * 2011-11-28 2014-12-03 宝山钢铁股份有限公司 Low-alloy steel used for oil well pipe with carbon dioxide corrosion resistance and manufacturing method thereof
DE102015217399A1 (en) * 2015-09-11 2017-03-16 Thyssenkrupp Ag Bourdon tube for motor vehicles and a method for producing a Bourdon tube

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GB839063A (en) * 1957-02-11 1960-06-29 Fagersta Bruks Ab Improvements relating to steel for welding or cold working
US3741822A (en) * 1971-07-14 1973-06-26 North Star Steel Co High strength steel
US4256517A (en) * 1978-01-09 1981-03-17 Republic Steel Corporation Welded alloy casing
DE2900022C3 (en) * 1979-01-02 1981-12-03 Estel Hoesch Werke Ag, 4600 Dortmund Process for producing profiles
US4282047A (en) * 1979-08-29 1981-08-04 Kawasaki Steel Corporation Method of producing steel pipe material for oil well
JPS5937328B2 (en) * 1980-09-05 1984-09-08 新日本製鐵株式会社 Method for producing hot-rolled steel for steel pipes with excellent sour resistance properties
US4394189A (en) * 1981-05-08 1983-07-19 Lone Star Steel Company High performance tubulars for critical oil country applications and improved process for their preparation
US4354882A (en) * 1981-05-08 1982-10-19 Lone Star Steel Company High performance tubulars for critical oil country applications and process for their preparation
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DE3127373C2 (en) * 1981-07-09 1985-08-29 Mannesmann AG, 4000 Düsseldorf Process for the manufacture of seamless steel tubes for the petroleum industry
CS330783A2 (en) * 1982-07-09 1984-06-18 Mannesmann Ag Zpusob vyroby plechu s jemnozrnnou strukturou z nizce legovane oceli pro vyrobu trub velkeho prumeru

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DE3415590A1 (en) 1985-10-31
CA1239332A (en) 1988-07-19
JPS60234952A (en) 1985-11-21
EP0160616A2 (en) 1985-11-06
ATE38059T1 (en) 1988-11-15
DE3415590C2 (en) 1987-11-12
EP0160616A3 (en) 1986-12-30
US4631095A (en) 1986-12-23
BR8501925A (en) 1985-12-24

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